Problematic Ar F -Alkynyl Coupling with Fluorinated Aryls. From Partial Success with Alkynyl Stannanes to Efficient Solutions via Mechanistic Understanding of the Hidden Complexity.

The synthesis of aryl-alkynyl compounds is usually achieved via Sonogashira catalysis, but this is inefficient for fluorinated aryls. An alternative method reported by Shirakawa and Hiyama, using alkynylstannanes and hemilabile PN ligands, works apparently fine for conventional aryls, but it is also poor for fluorinated aryls. The revision of the unusual literature cycle reveals the existence and nature of unreported byproducts and uncovers coexisting cycles and other aspects that explain the reasons for the conflict. This knowledge provides a full understanding of the real complexity of these aryl/alkynylstannane systems and the deviations of their evolution from that of a classic Stille process, providing the clues to design several very efficient alternatives for the catalytic synthesis of the desired Ar F -alkynyl compounds in almost quantitative yield. The same protocols are also very efficient for the catalytic synthesis of alkynyl-alkynyl' hetero- and homocoupling.